Synthesis and Thermal Rearrangement of Tetramethyldisilane-bridged Bis(cyclopentadienyl) Diiron Complexes with Bis(phosphine)Substitution

Photolysis of [Me2SiSiMe2)[C5H4Fe(CO2)]2with a series of bis(phosphine)ligands Ph2P(CH2)n PPh2(n=1-4) leads to the formation of the corresponding diiron complexes with intramolecular and intermolecular bis(phosphine) substitution.When these complexes were heated in refluxing xylene.only in the complexes with intermolecular bis(phosphine )substitution the thermal rearrangement reaction occurred.     

Synthesis and Crystal Structure of Bis（2-acetylpyridine thiosemicarbazonato）-indium（iii） Perchlorate Hydrate

The title complex bis(2-acetylpyridine thiosemicarbazonato)-indium(iii) perchlo-rate hydrate has been synthesized by the reaction of 2-acetylpyridine thiosemicarbazide(L) with indium(iii) perchlorate,and its structure was characterized by elemental analysis,IR and single-crystal X-ray diffraction.The crystal of the title compound([In(C8H9N4S)2]ClO4·H2O) belongs to monoclinic,space group P21/c with a = 12.6438(18),b = 12.6259(18),c = 15.116(2) nm,β = 105.800(2)°,Z = 4,V = 2321.9(6) nm3,Mr = 618.79,Dc = 1.770 g/cm3,μ = 1.359 mm-1,F(000) = 1240,R = 0.0265 and wR = 0.0675.X-ray analysis indicates that various intriguing hydrogen patterns involving both the solvent intermedia and polyatomic counterions play crucial roles in the self-assembly of functional supramolecules.     

配合物(ArO)2Yb(NPh2)2K(THF)4(Ar=C6H2-t-Bu3-2,4,6)的合成、分子结构和催化行为

Reaction of anhydrous YbC13 with 2 equiv, of sodium 2,4,6-tri-tert-butylphenoxide (ArONa, Ar=C6H2-t-Bu3-2,4,6) and 2 equiv, of potassium diphenyl amide in THF afforded the first bis(aryloxo) amido-lanthanide complex of (ArO)2Yb(NPh2)2K(THF)4 (1). In 1, the ytterbium and potassium were bridged via diphenyl amido ligands.The ytterbium metal center was coordinated to two oxygen atoms of aryloxide ligands and two nitrogen atoms of diphenyl amido ligands in a conventional distorted tetrahedral fashion, while the potassium interacted in η^2-fashion with two phenyl rings of the diphenyl amido ligands besides four THF molecules. 1 displayed moderate catalytic activities for the polymerization of methyl methacrylate and acrylonitrile.     

Synthesis,Crystal Structure and Antimicrobial Activity of {[Bis(pyridine-κN)bis(3,5-dinitrosalicylato κ-O,O')Zn(Ⅱ)][bis(pyridine-κN)Zn(Ⅱ)]}

A novel {[bis(pyridine-κN)bis(3,5-dinitrosalicylato κ-O,O')Zn(Ⅱ)][bis(pyridine-κN)Zn(Ⅱ)]}(C_(34)H_(24)N_8O_(14)Zn_2) was synthesized by a self-assemble method at room temperature. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the monoclinic system, space group P2_1/n with a = 12.2156, b = 13.5696, c = 22.5602 ?, β = 90.061o, Z = 4 and V = 3739.6(3) ?~3. The new 1D binuclear coordination polymer {[bis(py-κN)bis(3,5-dinitrosal κ-O,O′) Zn(Ⅱ)][bis(py-κN)Zn(Ⅱ)]} resulted from two different types of moieties. The polymer [bis(py-κN)bis(3,5-dinitrosal κ-O,O′)Zn(Ⅱ)] unit is connected with [bis(py-κN) Zn(Ⅱ)] by zigzag topology. One zinc(Ⅱ) cation has a six-fold coordination environment, in which the metal atom is connected with four oxygen atoms of two 3,5-dinitrosalicylic acids to form equatorial bonds and two nitrogen atoms of pyridine to generate the axial bonds. Other four-fold nucleus contain two Zn–O bonds from different 3,5-dinitrosalicylic acids and two bonds with the Natom of pyridine. Antimicrobial assay results indicated that the compound showed moderate activities against different bacterial and fungal strains.     

Synthesis,Crystal Structure and Antitumor Activity of a Na(Ⅰ) Coordination Polymer Based on 2-Propyl-4,5-imidazoledicarboxylic Acid and 1,10-Phenanthroline Ligands

A new Na(I) coordination polymer, [Na2(Hpimdc)(H2 pimdc)(phen)2]n(1), has been synthesized by the reaction of NaOH with 2-propyl-4,5-imidazoledicarboxylic acid(H3 pimdc)and 1,10-phenanthroline(phen). The Na(I) coordination polymer 1 was characterized by single-crystal X-ray diffraction analysis and elemental analysis. In 1, the bridged ligand H3 pimdc adopts two modes(singly deprotonated and doubly deprotonated) to coordinate with the Na(I) ion.The Na(1) ion is six-coordinated with three N atoms from a phen ligand and a H2 pimdc ligand,three O atoms from a Hpimdc ligand and two other different H2 pimdc ligands. The Na(2) ion is also six-coordinated with three N atoms from a phen ligand and a Hpimdc ligand, three O atoms from a H2 pimdc ligand and other two different Hpimdc ligands. Complex 1 exhibits a 1 D chain structure built up by μ-H2 pimdc-and μ-Hpimdc2-ligands. The antitumor activities of complex 1 against human SGC7901, A549 and H08910 cells have been tested.     

Synthesis of Dendrimer-supported Chiral Bis(oxazoline) Ligands and Their Applications in Aldol Reaction via Aqueous Media

Chiral bis(oxazoline) ligands have been applied in many enatioselective reactions. Recently, studies of the immobilization of bis(oxazoline) on both soluble and insoluble supports have been of great interest. Among the different methods to anchor the homogeneous catalysts, a soluble, polymer-supported catalyst usually achieves higher stereoselectivity and activity because the catalysis can be separated and recycled via simple methods such as solvent precipitation. Dendrimers are highly branche…     

A One-dimensional Coordination Polymer of Copper(Ⅱ) and Bis(4,6-dimethyl-2-pyrimidinethiolato)methane

Reaction of bis(4,6-dimethyl-2-pyrimidinethiolato)methane(bpytm) with CuCl2·4H2O in a mixed methanol/dichloromethane solution gave a one-dimensional coordina-tion polymer [CuCl2(μ-bpytm)]n which was characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic,space group P21/c with a=16.9433(5),b=13.6986(4),c=7.8434(2),β=100.371(2)°,V=1790.71(9)3,Z=4,Mr=426.86,Dc=1.583 g/cm3,μ(MoKα)=1.751mm-1,F(000)=868,S=1.025,the final R=0.0399 and wR=0.0924 for 2538 observed reflections with Ⅰ2σ(Ⅰ) and 206 variables.The neutral coordination polymer is constructed by the bidentate thioether ligands to link adjacent copper atoms.Each copper atom is bridged by two adjacent nitrogen atoms of bpytm ligands and terminally bonded by two chloride atoms to form a squareplanar coordination geometry.The average Cu-N and Cu-Cl bond lengths are 2.025(2) and 2.234(1),respectively.     

A 2D Wavy Parquet Architecture Based on the Biphenyl-3,3’,4,4’-tetracarboxylic Acid and Bis(2-benzimidazole)alkanes Ligands

A double-T-shaped ligand (H4BPTC) and bis(2-benzimidazole)alkanes as the spacers have been firstly used to direct the assembly of a 2D coordination polymer with wavy parquet network topology, [Zn(BPTC)0.5(H2C2EIm)(H2O)]n (1, C24H18ZnN4O5, Mr = 507.79, H4BPTC = biphenyl-3,3',4,4'-tetracarboxylic acid, H2C2EIm = 2,2'-(1,2-ethanediyl)-bis(1H-benzi- midazole), which was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/n with a = 1.1844(5), b = 1.4019(5), c = 1.4026(5) nm, β = 108.359(5)°, V = 2.2104(15) nm3, Z = 4, Dc = 1.526 g/cm3, μ(MoKα) = 1.156 mm-1, F(000) = 1040, S = 1.038, the final R = 0.0427 and wR = 0.0793 for 3834 reflections with I > 2σ(I). The compound units are linked through BPTC ligands into a wavilness parquet 2D layer and further connected into a 3D framework via π-π packing interactions between the adjacent H2C2EIm ligands and weak N-H…O hydrogen bonding between uncoordinated carboxylate and the nitrogen atoms of H2C2EIm as well as the free water molecules.     

Hydrothermal Syntheses,Crystal Structures and Luminescence Properties of Zn(Ⅱ) and Cu(Ⅱ) Complexes Based on 2,2'-((Sulfonylbis(4,1-phenylene))bis(oxy))diacetic Acid

The 2,2'-((sulfonylbis(4,1-phenylene))bis(oxy))diacetic acid(H2L) and 4,4'-bipyridine(4,4'-bipy) are employed as organic ligands to react with metal salts to obtain two new metal-organic frameworks(MOFs), namely [M2L2(4,4'-bipy)](M = Zn(1), Cu(2)). They have been successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction reveals that two complexes are isostructural and crystallize in orthorhombic system with space group Pbcn. All L^2- ligands bridge metal ions to form an infinite 1D Z-shaped chain along the a axis. Then through 4,4'-bipy, contiguous Z-shaped chains are linked to form a 2D layer structure. The luminescent studies of the H2L ligand and complex 1 in the solid state and thermogravimetric analyses(TGA) of two complexes are investigated.     

Syntheses,Structures and Vitro Anticancer Activities of μ_2-O-and μ_2-Dimethylglyoximato-bridged μ_3-O-Tris[di(m-fluorobenzyl)tin] Bis(dimethylglyoximate)

μ_2-O-and μ_2-dimethylglyoximato-bridged μ_3-O-tris[di(m-fluorobenzyl)tin] bis(dimethylglyoximate)(1) has been synthesized by the reaction of di(m-fluorobenzyl)tin dichloride with dimethylglyoxime. Complex 1 was characterized by means of IR,~1H NMR,elemental analysis and X-ray diffraction. It crystallizes in orthorhombic system,space group Pna21 with a = 2.22172(12),b = 1.05566(6),c = 2.15577(12) nm,V = 5.0561(5) nm~3,Z = 4,C_(50)H_(50)F_6N_4O_6Sn_3,Mr = 1273.01,Dc = 1. 6721 g/cm3,μ_(MoΚα) = 15.44 cm~(-1),F(000) = 2520,R = 0.0281 and wR = 0.0683. The stabilities,orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been investigated with the quantum chemistry calculation. The properties of thermogravimetric and vitro anticancer activities of the compound have been discussed.     

Studies on the Biomimetic Oxidation Catalyzed by the Model Compound of Cytochrome P-450 (Ⅶ) The Influence of the Axial Ligand X in TPPFe(Ⅲ)X on Its Catalytic Properties for the Oxygenation of Cyclohexane

In the study of cyclohexane monoxygenation with PhIO catalyzed by TPPFe( Ⅲ )X, we found the Influence of different axial ionic ligands X (X = F, Cl, Br, I, SCN, OR, R, CH,3, C2H6, (CH3)2CH, (CH2)3C)in TPPFe( Ⅲ )X on the oxidation products distribution and the yields of cyclohexanol. This paper deals with the linear relationship between the catalytic activity of TPPFe(Ⅲ)X and both the electronic or/ and steric effects of the axial ligands OR in TPPFe(Ⅲ)OR on its catalytic activity.     

Construction of a New Two-fold Interpenetrated Three-dimensional Cobalt(Ⅱ) Coordination Polymer Based on 2,5-Thiophenedicarboxylic Acid and Bis(imidazol-1-yl)methane

A cobalt coordination polymer, {[Co_2(tdc)_2(bimm)_2]·(3 DMF)}n, was synthesized based on 2,5-thiophenedicarboxylic acid(H2 tdc) and bis(imidazol-1-yl)methane(bimm) mixed ligands. The asymmetric unit of the complex contains two Co~(~(2+)) cations, two tdc2-dianions, two neutral bimm ligands, and three free DMF molecules. In the complex, deprotonated tdc2-dianions alternately bridge the adjacent Co~(2+) cations to generate chains, which are further connected by the flexible bimm ligands to form a 3 D structure containing adamantanoid-like subunits. In topology, the structure of 1 represents a 4-connected uninodal two-fold interpenetrated dia(66) topology. Moreover, the solid UV-Vis absorption spectra of the complex have also been investigated.     

Unusual Coordination Mode of Tetradentate Diiminedioxime Ligand in a Mononickel(Ⅱ) Complex:Synthesis,Characterization, and Computational Study

In this work, it is found that 1,8-dihydroxyimino-1,2,7,8-tetraphenyl-3,6-diazocta-2,6-diene(~(Ph)doenH_2) could react with nickel(Ⅱ) salt to yield a mononickel complex Ni(Phdoen)(1) with unusual [2N2O]-coordinated mode, while the analogous diimine-dioxime ligands usually form the [4N]-coordinated mode. The novel complex 1 has been carefully characterized by ~1H NMR, elemental analysis, and X-ray diffraction structure analysis. The influences of the coordination modes on the structures and redox properties have been further investigated. Theoretical investigations revealed that the different coordination modes were ascribed to the thermodynamic properties of ligands.     

Copolymerization of Ethylene with 10-Undecen-1-ol Using Highly Active Vanadium(Ⅲ) Precatalysts Bearing Bis(imino)pyrrolyl Ligands

The copolymerizations of ethylene with 10-undecen-1-ol have been investigated using vanadium precatalysts, bis(imino)pyrrolyl vanadium(III) complexes 1-3, 2,5-C4H2N(CH=NR)2VCl2(THF)2 [R = C6H5(1), 2,6-iPr2C6H3(2), C6F5(3)], and the iminopyrrolyl and β-diketiminate ones for comparison. The polar monomer was pretreated by diethylaluminium chloride(present also as the cocatalyst) before the copolymerization. The monomer reactivity ratios were evaluated using the Fineman-Ross method. The ligand structure considerably influenced the catalytic activity and tolerance towards the polar monomer, the polar monomer incorporation and the molecular weights of the resultant copolymers. The bis(imino)pyrrolyl vanadium complexes exhibited promising catalytic performance for the copolymerization, and a high catalytic activity up to 3.84 kg/mmolv·h with a high comonomer incorporation of 14.0 mol% was achieved by complex 3 under mild conditions.     

Binuclear Aluminum Complexes Supported by Linked Bis(β-diketiminate) Ligands for Ring-Opening Polymerization of Cyclic Esters

Binuclear aluminum alkyl complexes 2a–4g supported by linked bis(β-diketiminate) ligands were synthesized via the reaction of AlEt_3 or AlMe_3 and the corresponding proligand in a 2:1 molar ratio with moderate yields. The isolated complexes were well-characterized by ~1H-NMR, ~(13)C-NMR and elemental analysis. The binuclear nature of aluminum complex 2b was further confirmed by an X-ray diffraction study. All complexes 2a–4g could efficiently initiate the ring-opening polymerization(ROP) of ε-caprolactone in toluene. The substituents at the aromatic rings and the linker unit in the auxiliary ligands exerted significant influence on the catalytic behavior of the investigated aluminum complexes. Complex 4g(R~1 = R~2 = Cl) containing propylenyl bridging unit exhibited the highest catalytic activity among these complexes, which might be attributed to the increased electrophilicity of the metal center as well as more opened coordination sphere. The molecular weights of obtained poly(ε-caprolactone)s deviating considerably from the theoretical values indicated that the ROP of ε-caprolactone by complexes 2a–4g was not well-controlled, which was also judged from the broad molecular weight distributions(MWD = 1.47-2.47) of produced poly(ε-caprolactone)s. These complexes proved to be inactive toward the polymerization of rac-lactide alone. In the presence of alcohol the polymerization occurred, which was actually initiated by the decomposition species of the aluminum complex upon the treatment with isopropanol.     

Propylene Polymerization Catalyzed by Bis(R_3-indenyl) Zirconium Dichloride/Aluminoxane──Synthesis of Metallocenes and Influence ofSolvent Polarity on Polymerization

Three unbridged metallocenes, bis(2,4,7-Me3-indenyl)zirconium dichloride(1) , bis(2-Me-4, 7-Et2-indenyl)zirconium dichloride (2) and bis (2, 4, 6-Me3-indenyl) zirconium dichloride (3) were synthesized. The effect of solvent polarity on propylene polymerization catalyzed by the metallocenes in the presence of methylaluminoxane(MAO) and triisobutylaluminum(TIBA) was investigated in the toluene/CH2Cl2 mixed solvent. Changing the solvent polarity was found to influence the catalytic activity, polymer molecular weight and stereospecificity of the catalysts. The changes in the position of the substituents on the ligand caused the different responses of the catalyst to the changes in solvent polarity. The isotactic stereosequence of polypropylene was found to increase with the increase in the polarity of the reaction medium.     

DFT Studies on Second-order Nonlinear Optical Response of Ir(C∧N)2(pic)Complexes

Density flmctional theory(DFT)was employed to calculate the geometrical structures,UV-Vis absorption spectra and second-order nonlinear optical(NLO)properties of a family of iridium(Ⅲ)complexes,which possess of different cyclometallated ligands(C∧N)and ancillary ligands[pyridme-2-carboxylate(pic)].It was found that the mo-dification of the LUMO energy levels was achieved by changing pic ligands and the energy gaps between the HOMO and LUMO were notably increased or decreased.In addition,the degree of conjugation was significantly changed with the substituent groups varied,which led to that the first hyperpolarizabilityβcould be effectively modulated.Through the analysis of time-dependent DFT(TD-DFT)results,we predicted that these studied complexes withπ→π^*charge transfer was beneficial to the large second-order NLO properties.Therefore,we hope that these studied iridium(III)complexes can be considered as versatile second-order NLO materials.     

Synthesis,Crystal Structure and Physical Properties of a Novel Cadmium(Ⅱ) Supramolecular 3D Framework

A new inorganic-organic hybrid cadmium(Ⅱ) complex [Cd2(H1/2C4BIm)2(CH3COO)]nhas been prepared by a hydrothermal reaction,and characterized by fluorescence,IR,TGA,and single-crystal X-ray diffraction analysis.In its crystal structure,there are two kinds of coordinating forms for those Cd(Ⅱ) ions.One is that the Cd(Ⅱ) ion is coordinated by one carboxylate oxygen atom from one acetate oxygen ligand and three benzimidazole nitrogen atoms from three 2,2’-(1,4-butanediyl)bis(1H-benzimidazole)(H2C4BIm) ligands,and the other is that the Cd(Ⅱ) ion is coordinated by four benzimidazole nitrogen atoms from four H2C4 BIm ligands to furnish two distorted tetrahedral coordination geometries.It exhibits a beautiful structure for a 2D layer and a 3D network,with its four-connecting nodes provided by the H2C4 BIm ligands.Furthermore,this complex shows intense luminescent property at room temperature.In [Cd2(H2C2BIm)2(C9H6O4)2]n,the H2C2 BIm ligand lost the role as a bridging ligand because of the shorter alkyl chain compared with that of H2C4 BIm ligand.     

Synthesis,Crystal Structure and Antimicrobial Activity of a New Ternary Copper(Ⅱ) Complex with p-Chlorophenoxyacetic Acid and 2-Amino Benzothiazole

A novel ternary complex of Cu(pcpa)2(aben)2 (pcpa=p-chlorophenoxyacetic acid anion,aben=2-amino benzothiazole) was synthesized by the reaction of copper acetate,2-amino benzothiazole and p-chlorophenoxyacetic acid.Elemental analysis,IR,UV and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure.The crystal crystalli-zes in the monoclinic system,space group C2/c with a=25.795(4),b=7.384(3),c =17.741(6),β=107.47(2)°,C30H24Cl2CuN4O6S2,Mr=735.09,V=3223.2(18) 3,Z=4,Dc=1.515 Mg/m3,λ(MoKα)=0.71073 ,μ=1.022 mm-1,F(000)=1500,the final R=0.0464 and wR=0.1244.A total of 3218 unique reflections were collected,of which 2228 with I 2σ(I) were observed.The Cu(II) atom is four-coordinated with two carboxylate oxygen atoms of the two pcpa ligands and two nitrogen atoms in thiazole rings of two aben ligands.The analysis of crystal structure shows intermolecular and intramolecular hydrogen bonds between amino-nitrogen atoms of the two aben ligands and carboxylate oxygen atoms of the two pcpa ligands.The antimicrobial properties of the title complex and its two free ligands were tested against representative bacterial and fungal strains.Results show that the antibacterial activity of the complex is less than or equal to that of 2-amino benzothiazole,but for yeasts and moulds,it exhibits excellent inhibitory effect better than that of its two free ligands.     

Synthesis and Crystal Structure of a New Complex Zn(Ⅱ)L_2·2CH_3OH(H_2L = 4-Chloro-2-(2,3-dihydro-1H-benzoimidazol-2-yl)-phenol)

A new complex Zn(Ⅱ)L2·2CH3OH(H2L = 4-chloro-2-(2,3-dihydro-1H-ben-zoimi-dazol-2-yl)-phenol) has been prepared and characterized by single-crystal X-ray diffraction analysis and elemental analysis.The crystal is of triclinic system,space group P1 with a = 9.2905(10),b = 10.3555(13),c = 14.9590(14) ,α = 101.0340(10),β = 101.261(2),γ = 99.1660(10)o,V = 1356.1(3) 3,Z = 2,C28H24Cl2N4O4Zn,Mr = 616.78,Dc = 1.510 g/cm3,μ = 1.145 mm·1,F(000) = 632,the final R = 0.0379 and wR = 0.0830 for 3606 observed reflections with I 2σ(I).The Zn(Ⅱ) atom presents a distorted square pyramidal coordination involving two H2L ligands.The hydrogen bonds and π···π stacking interactions extend the complex into a two-dimensional framework.